Hydrogen/Deuterium Exchange Mass Spectrometry for Probing the Isomeric Forms of Oleocanthal and Oleacin in Extra Virgin Olive Oils
Reversed-phase liquid chromatography and electrospray ionization with Fourier-transform single and tandem mass spectrometry (RPLC-ESI-FTMS and FTMS/MS) were employed for the structural characterization of oleocanthal (OLEO) and oleacin (OLEA), two of the most important bioactive secoiridoids occurri...
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| Format: | Article |
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MDPI AG
2023-02-01
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| Series: | Molecules |
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| Online Access: | https://www.mdpi.com/1420-3049/28/5/2066 |
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| author | Ramona Abbattista Ilario Losito Graziana Basile Andrea Castellaneta Giovanni Ventura Cosima Damiana Calvano Tommaso R. I. Cataldi |
| author_facet | Ramona Abbattista Ilario Losito Graziana Basile Andrea Castellaneta Giovanni Ventura Cosima Damiana Calvano Tommaso R. I. Cataldi |
| author_sort | Ramona Abbattista |
| collection | DOAJ |
| description | Reversed-phase liquid chromatography and electrospray ionization with Fourier-transform single and tandem mass spectrometry (RPLC-ESI-FTMS and FTMS/MS) were employed for the structural characterization of oleocanthal (OLEO) and oleacin (OLEA), two of the most important bioactive secoiridoids occurring in extra virgin olive oils (EVOOs). The existence of several isoforms of OLEO and OLEA was inferred from the chromatographic separation, accompanied, in the case of OLEA, by minor peaks due to oxidized OLEO recognized as oleocanthalic acid isoforms. The detailed analysis of the product ion tandem MS spectra of deprotonated molecules ([M-H]<sup>−</sup>) was unable to clarify the correlation between chromatographic peaks and specific OLEO/OLEA isoforms, including two types of predominant dialdehydic compounds, named <i>Open Forms II</i>, containing a double bond between carbon atoms C8 and C10, and a group of diasteroisomeric closed-structure (i.e., cyclic) isoforms, named <i>Closed Forms I</i>. This issue was addressed by H/D exchange (HDX) experiments on labile H atoms of OLEO and OLEA isoforms, performed using deuterated water as a co-solvent in the mobile phase. HDX unveiled the presence of stable di-enolic tautomers, in turn providing key evidence for the occurrence, as prevailing isoforms, of <i>Open Forms II</i> of OLEO and OLEA, different from those usually considered so far as the main isoforms of both secoiridoids (having a C=C bond between C8 and C9). It is expected that the new structural details inferred for the prevailing isoforms of OLEO and OLEA will help in understanding the remarkable bioactivity exhibited by the two compounds. |
| first_indexed | 2024-03-11T07:18:07Z |
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| issn | 1420-3049 |
| language | English |
| last_indexed | 2024-03-11T07:18:07Z |
| publishDate | 2023-02-01 |
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| series | Molecules |
| spelling | doaj.art-f716dc00ea16454fba7638c3993924a12023-11-17T08:11:32ZengMDPI AGMolecules1420-30492023-02-01285206610.3390/molecules28052066Hydrogen/Deuterium Exchange Mass Spectrometry for Probing the Isomeric Forms of Oleocanthal and Oleacin in Extra Virgin Olive OilsRamona Abbattista0Ilario Losito1Graziana Basile2Andrea Castellaneta3Giovanni Ventura4Cosima Damiana Calvano5Tommaso R. I. Cataldi6Dipartimento di Chimica, Università degli Studi di Bari “Aldo Moro”, Via E. Orabona 4, 70126 Bari, ItalyDipartimento di Chimica, Università degli Studi di Bari “Aldo Moro”, Via E. Orabona 4, 70126 Bari, ItalyDipartimento di Chimica, Università degli Studi di Bari “Aldo Moro”, Via E. Orabona 4, 70126 Bari, ItalyDipartimento di Chimica, Università degli Studi di Bari “Aldo Moro”, Via E. Orabona 4, 70126 Bari, ItalyDipartimento di Chimica, Università degli Studi di Bari “Aldo Moro”, Via E. Orabona 4, 70126 Bari, ItalyDipartimento di Chimica, Università degli Studi di Bari “Aldo Moro”, Via E. Orabona 4, 70126 Bari, ItalyDipartimento di Chimica, Università degli Studi di Bari “Aldo Moro”, Via E. Orabona 4, 70126 Bari, ItalyReversed-phase liquid chromatography and electrospray ionization with Fourier-transform single and tandem mass spectrometry (RPLC-ESI-FTMS and FTMS/MS) were employed for the structural characterization of oleocanthal (OLEO) and oleacin (OLEA), two of the most important bioactive secoiridoids occurring in extra virgin olive oils (EVOOs). The existence of several isoforms of OLEO and OLEA was inferred from the chromatographic separation, accompanied, in the case of OLEA, by minor peaks due to oxidized OLEO recognized as oleocanthalic acid isoforms. The detailed analysis of the product ion tandem MS spectra of deprotonated molecules ([M-H]<sup>−</sup>) was unable to clarify the correlation between chromatographic peaks and specific OLEO/OLEA isoforms, including two types of predominant dialdehydic compounds, named <i>Open Forms II</i>, containing a double bond between carbon atoms C8 and C10, and a group of diasteroisomeric closed-structure (i.e., cyclic) isoforms, named <i>Closed Forms I</i>. This issue was addressed by H/D exchange (HDX) experiments on labile H atoms of OLEO and OLEA isoforms, performed using deuterated water as a co-solvent in the mobile phase. HDX unveiled the presence of stable di-enolic tautomers, in turn providing key evidence for the occurrence, as prevailing isoforms, of <i>Open Forms II</i> of OLEO and OLEA, different from those usually considered so far as the main isoforms of both secoiridoids (having a C=C bond between C8 and C9). It is expected that the new structural details inferred for the prevailing isoforms of OLEO and OLEA will help in understanding the remarkable bioactivity exhibited by the two compounds.https://www.mdpi.com/1420-3049/28/5/2066secoiridoidsoleocanthaloleacinolive oilhigh resolution mass spectrometryH/D exchange |
| spellingShingle | Ramona Abbattista Ilario Losito Graziana Basile Andrea Castellaneta Giovanni Ventura Cosima Damiana Calvano Tommaso R. I. Cataldi Hydrogen/Deuterium Exchange Mass Spectrometry for Probing the Isomeric Forms of Oleocanthal and Oleacin in Extra Virgin Olive Oils Molecules secoiridoids oleocanthal oleacin olive oil high resolution mass spectrometry H/D exchange |
| title | Hydrogen/Deuterium Exchange Mass Spectrometry for Probing the Isomeric Forms of Oleocanthal and Oleacin in Extra Virgin Olive Oils |
| title_full | Hydrogen/Deuterium Exchange Mass Spectrometry for Probing the Isomeric Forms of Oleocanthal and Oleacin in Extra Virgin Olive Oils |
| title_fullStr | Hydrogen/Deuterium Exchange Mass Spectrometry for Probing the Isomeric Forms of Oleocanthal and Oleacin in Extra Virgin Olive Oils |
| title_full_unstemmed | Hydrogen/Deuterium Exchange Mass Spectrometry for Probing the Isomeric Forms of Oleocanthal and Oleacin in Extra Virgin Olive Oils |
| title_short | Hydrogen/Deuterium Exchange Mass Spectrometry for Probing the Isomeric Forms of Oleocanthal and Oleacin in Extra Virgin Olive Oils |
| title_sort | hydrogen deuterium exchange mass spectrometry for probing the isomeric forms of oleocanthal and oleacin in extra virgin olive oils |
| topic | secoiridoids oleocanthal oleacin olive oil high resolution mass spectrometry H/D exchange |
| url | https://www.mdpi.com/1420-3049/28/5/2066 |
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